New phosphorus-containing quinone derivatives

Article abstract of DOI:10.1002/hc.21028

A variety of new aromatic diols substituted with two (similar and different) phosphorus groups were synthesized via the Michael-type addition of a Pi￡H bond containing reagents to p-benzoquinone, reoxidation and the subsequent addition of a second phosphorus unit. In all studied cases, 2,3-substituted products were obtained exclusively. The resulting hydroquinone derivatives were further investigated regarding rearrangements under basic conditions.

Full text of DOI:10.1002/hc.21028

Heteroatom Chemistry
Volume 00, Number 0, 2012
New Phosphorus-Containing Quinone
Derivatives
Patrick Mu¨ller,1 Yana Bykov,1 Olaf Walter,2 and Manfred Do¨ring,1,∗
1Institute of Catalysis Research and Technology, Karlsruhe Institute of Technology, 76344
Eggenstein-Leopoldshafen, Germany
2European Commission Joint Research Centre, Institute for Transuranium Elements, 76344
Eggenstein-Leopoldshafen, Germany
Received 11 January 2012; revised 5 April 2012
quinone derivatives as dyes and biologically active
ABSTRACT: A variety of new aromatic diols sub-
compounds [12–14]. As a relatively new field of use,
stituted with two (similar and different) phospho-
phosphorus-carrying quinones recently gained im-
rus groups were synthesized via the Michael-type
portance as flame-retardant additives, for instance,
addition of a P H bond containing reagents to p-
for epoxy resins [15]. P-containing hydroquinones
benzoquinone, reoxidation and the subsequent ad-
as comonomers for inherent flame-retardant poly-
dition of a second phosphorus unit. In all studied
mers are of special interest in this connection and
cases, 2,3-substituted products were obtained exclu-
therefore the subject of current research [16–22].
sively. The resulting hydroquinone derivatives were
In general, most phosphorus reagents in a
further investigated regarding rearrangements under
reaction with, e.g., p-benzoquinone, undergo the
ꢀ
C
basic conditions.
2012 Wiley Periodicals, Inc. Het-
Michael-type addition, resulting in aromatic, C-
phosphorylated hydroquinone derivatives. Some
reagents also perform O-phosphorylation [12]. For
phosphine- and phosphinoxide-type compounds, di-
and trialkyl phosphinoxides are reported to un-
dergo mono-C-addition [12], in contrast to pri-
mary phosphines (H2P-R), which directly reduce
p-benzoquinone to hydroquinone, yielding RPH-
HPR [23]. In the case of phosphite-type reagents,
mono- and di-C-addition takes place as well as O-
phosphorylation, depending on the conditions [12],
whereas phosphate-type compounds normally do
not react with p-benzoquinone [13].
eroatom Chem 00:1–12, 2012; View this article online at
wileyonlinelibrary.com. DOI 10.1002/hc.21028
INTRODUCTION
Addition reactions of phosphorus-containing com-
pounds to unsaturated systems have been thor-
oughly investigated throughout the past decades
[1–4]. The phospha-Michael reaction, especially, has
been the topic of a great variety of recent studies
regarding different types of substrates, different re-
action conditions, and diastereoselectivity [4–11].
As such, the reaction behavior of phosphorus-
containing reagents toward quinones has been in-
vestigated thoroughly due to the significance of
However, previous work predominantly focuses
on monosubstituted phosphorus quinones. This pa-
per presents a novel approach to new quinone
derivatives carrying two similar or different phos-
phorus units.
Correspondence to: Manfred Do¨ring; e-mail: manfred.doering@
kit.edu.
Contract grant sponsor: German Research Foundation.
Contract grant numbers: DFG SCHA 730/10-1, DFG DO 453/6-1,
RESULTS AND DISCUSSION
The reaction of diphenyl phosphite with p-
benzoquinone resulted in both mono- and
DFG AL 474/14-1 and SCHA 730/11-1, DO 453/7-1, PO 575/11-1.
c
ꢀ
2012 Wiley Periodicals, Inc.
1

2
Mu¨ller et al.
O
O
OH
O
P(OPh)2
HPO(OPh)2
OH
1a
p-Benzoquinone
O
O
O
OH
O
P(OPh)2
P(OPh)2
HPO(OPh)2
P(OPh)2
OH
2a
O
SCHEME 1 Reaction of diphenyl phosphite with p-benzoquinone.
disubstituted p-hydroquinone derivatives (PhO)2PO-
HQ (1a) and (PhO)2PO-2-HQ (2a) that can be
explained by an in situ reoxidation of the former by
unreacted p-benzoquinone (Scheme 1). This is in
agreement with the results published for dimethyl
phosphite [24] and 5,5-dimethyl-2-oxido-1,3,2-
dioxaphosphinan (DDPO; another phosphite-type
reactant), which also yielded both products in
the reaction with p-benzoquinone [20,25]. X-ray
analysis of the disubstituted (PhO)2PO-2-HQ (2a;
Scheme 1) revealed the phosphorus groups in
ortho-position (Fig. 1).
The reproduction of the procedure described
for the reaction of p-benzoquinone with DDPO
[20,25] also demonstrated formation of both the
monoadduct DDPO-HQ (1b) and ortho-substituted
diadduct DDPO-2-HQ (2b), as was indicated by
NMR spectroscopy. In 13C NMR the carbon directly
bound to the phosphorus atom (δ = 113.3 ppm in
DMSO-d6) appears as a doublet of doublets with the
the case of (PhO)2POHQ (1a) and (PhO)2PO-2-HQ
(2a), all hydroxyl groups form an intramolecular hy-
=
drogen bond with the close P O unit, whereas in
DDPO-2-HQ (2b), no such intramolecular interac-
tion is observed due to the bulkiness and restricted
flexibility of the heterocyclohexane units (Fig. 1). Yet
in the latter case, X-ray analysis revealed intermolec-
=
ular hydrogen bonds with the P O units of neighbor-
ing molecules.
For the reaction of p-benzoquinone with
phosphinate-type reactants (RHPO-ORꢁ) such as 6-
oxido-6H-dibenzo[c, e][1,2]oxaphosphinine (DOPO,
a widely used flame retardant by itself and building
block for advanced flame retardants) [16–22,28–31],
no in situ reoxidation is witnessed and the sole prod-
uct DOPO-HQ is obtained with a nearly quantitative
yield [16,17]. Formation of the diadduct (DOPO-2-
HQ, 3), as described in [32], could not be repro-
duced. A treatment following of DOPO-HQ with ex-
cess p-benzoquinone showed no reaction; therefore,
a kinetic explanation (an addition of DOPO being
much faster than a reoxidation) is unlikely.
To achieve an oxidation of DOPO-HQ, treat-
ment with activated MnO2 as a quick and easy lab-
scale method [33] was applied successfully, yielding
DOPO-BQ (4) as a bright orange solid (Scheme 2).
By a reaction of DOPO-BQ (4) with DOPO, DOPO-
2-HQ (3) was obtained in a good yield. Remarkably,
3 emerged as two diastereomers due to the chirality
of the phosphorus atoms. In addition, the bulkiness
of the phosphacycles in the ortho-position to each
other prevents a rotation of the substituents. Iso-
mer 3a shows a twisted overlapping of the DOPO
units, whereas in isomer 3b, they are congruently
staggered. In both cases, they are stabilized via π-
stacking, as evident by an X-ray structure analysis
1
2
ꢁ
coupling constants JC-P = 174.6 Hz and JC-P
=
9.7 Hz. The aromatic protons of DDPO-2-HQ (2b)
1
in the H NMR spectrum represent a triplet at 7.06
ppm with 4 JH-P = 3.75 Hz (DMSO-d6). In the case of
the para-substitution, a significantly larger coupling
3
constant JH-P (above 10 Hz) for the protons next
to the phosphorus units would be expected [26,27].
Furthermore, the ortho-structure is confirmed by X-
ray analysis (Fig. 1).
It is worth mentioning that the P C bond
formed in the reaction of diphenyl phosphite and p-
benzoquinone is notably shorter for the monoadduct
˚
(1a, 1.757 A) than in the case of the diadduct (2a,
˚
1.790–1.800 A). DDPO-2-HQ (2b) shows a corre-
˚
sponding P C bond length of 1.796–1.798 A. Fur-
thermore, X-ray structures clearly indicate that in
Heteroatom Chemistry DOI 10.1002/hc

New Phosphorus-Containing Quinone Derivatives
3
FIGURE 1 Molecular structures of (PhO)2PO-HQ (1a), (PhO)2PO-2-HQ (2a) (crystallizing as a pair of conformational isomers)
and DDPO-2-HQ (2b), validated by X-ray analysis (hydrogens omitted except on heteroatoms for reasons of clarity).
SCHEME 2 Syntheses of DOPO-BQ (4) and disubstituted p-hydroquinones DOPO-2-HQ (3), DOPOHQ-(PhO)2PO (5),
DOPO-HQ-DPhPO (6), and DOPO-HQ-DDPO (7).
Heteroatom Chemistry DOI 10.1002/hc

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Mu¨ller et al.
FIGURE 2 Molecular structures of diastereomers of DOPO-2-HQ (3) validated by X-ray analysis (hydrogens omitted except
on heteroatoms for reasons of clarity). In isomer a 6-6-π-stacking is present only between the two upper benzo units, whereas
isomer b (emerging in higher yield) is stabilized by π-stacking of both benzo units with the opposing ones.
TABLE 1 Lengths of P C and P O Bonds between
be ortho-substituted, according to X-ray and NMR
data, as was expected. The P C bonds of the deriva-
tives with different phosphorus units showed com-
parable lengths to the corresponding homogeneous
disubstituted hydroquinones (Table 1). X-ray analy-
sis (Fig. 3) also revealed the presence of intramolec-
ular hydrogen bonds for both H atoms of DOPO-
HQ-(PhO)2PO (5), whereas in DOPO-HQ-DPhPO (6),
only the hydroxyl group next to the DOPO unit
formed an intramolecular hydrogen bond. The other
did not due to sterical hindrances, forming rather,
intermolecular hydrogen bonds like both H atoms
of DOPO-HQ-DDPO (7).
Quinone and Phosphorus Units
P C
(DOPO Unit)
P C
(Phosphite)
Compound
(PhPO)2PO-HQ (1a)
((PhPO)2PO)2-HQ (2a)
DDPO-2-HQ (2b)
–
–
–
1.757
1.790–1.794
1.804–1.805
DOPO-2-HQ (3)
1.796–1.805
1.801
–
–
DOPO-BQ (4)
DOPO-HQ-(PhO)2PO (5)
DOPO-HQ-DPhPO (6)
DOPO-HQ-DDPO (7)
DDPO-2-HQ-rear (9b)
1.802
1.806
1.795
a
1.767–1.749b
–
1.807–1.808b
1.766–1.782
˚
Consideration of the distribution of local charges
in the mesomeric structures provides an explanation
for the formation of 2,3-substituted products from
the theoretical point of view. Although unsubstituted
p-benzoquinone does not favor any position, a nega-
tive charge can be localized not only at the carbonyl
All values are given in A (standard deviation < 0.005).
P
a
C Phosphine oxide: 1.808.
bstandard derivation 0.013.
(Fig. 2). However, the length of the newly formed
P C bond did not significantly differ between the
isomers (ranging from 1.796 to 1.805 A). Further-
more, intramolecular hydrogen bonds between the
protons of the hydroquinone hydroxyl groups and
˚
=
units but also at the P O unit (Scheme 3) in the case
of the phosphite-functionalized quinone. This leads
to an increased positivity of the ortho-position and,
hence, to a higher probability for nucleophilic ad-
dition. The effect is rather significant: although this
should preferably, but not exclusively lead to the or-
tho-products, practically no para-products were de-
tected in all cases studied.
=
the oxygens of the P O units are present in both
cases. The isomers obtained at a 1:1.5 ratio were
successfully separated by column chromatography
and show slightly different melting points (4–5◦C de-
viation) and chemical shifts in 31P NMR (1.15 ppm
deviation).
The reaction of p-benzoquinone with diphenyl
phosphite or DDPO led to the same products in
the presence of acetic acid [20,25] as well as un-
der neutral conditions. Nevertheless, when triethy-
lamine was used as a catalyst, a rearrangement
of the monoadduct occurred before reoxidation,
In addition,
a variety of disubstituted p-
hydroquinones with different phosphorus units were
synthesized by the reaction of DOPO-BQ (4) with
DDPO, diphenyl phosphite and diphenylphosphine
oxide (Scheme 2). All products 5–7 turned out to
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New Phosphorus-Containing Quinone Derivatives
5
FIGURE 3 Structure of DOPO-BQ (4), DOPO-HQ-(PhO)2PO (5), DOPO-HQ-DPhPO (6), and DOPO-HQ-DDPO (7), validated
by X-ray analysis (hydrogens omitted except on heteroatoms for reasons of clarity. 7 shown as one of two conformations).
=
SCHEME 3 Additional mesomeric structure of P O-functionalized p-benzoquinone.
effectively preventing the latter. The resulting
oxygen-substituted hydroquinone is unable to un-
dergo reoxidation for obvious reasons. Conse-
quently, no second addition takes place, and
(PhO)2PO-HQ-rear (8a) or DDPO-HQ-rear (8b), re-
spectively, emerged as the only product (Scheme 4).
For the reaction of dimethyl phosphite with p-
benzoquinone, traces of the rearranged product
were reported under neutral conditions [24].
(1b) with triethylamine resulted in the same rear-
ranged compounds 8a and 8b. Likewise, a refluxing
of DDPO-2-HQ (2b) with triethylamine in acetoni-
trile led to precipitation of DDPO-2-HQ-rear (9b) af-
ter cooling, with one of two phosphorus units being
relocated (Scheme 4 and Fig. 4). The newly formed
˚
P O bonds were significantly shorter (1.561 A for 8a,
˚
1.593–1.596 A for 9b) than the corresponding P C
bonds (Table 1).
In addition, a following treatment of the first iso-
lated monoadducts (PhO)2PO-HQ (1a) or DDPO-HQ
A treatment of DOPO-2-HQ (3) with triethy-
lamine resulted in DOPO-2-HQ-rear (10), with one
Heteroatom Chemistry DOI 10.1002/hc

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Mu¨ller et al.
SCHEME 4 Reaction of p-benzoquinone with phosphite-type compounds under different conditions.
FIGURE 4 Structure of (PhO)2PO-HQ-rear (8a) and DDPO-2-HQ-rear (9b), validated by X-ray analysis (hydrogens omitted
except on heteroatoms for reasons of clarity).
of two DOPO units being relocated (structure
similar to 9b). A rearrangement of the second
phosphorus unit did not take place. However, the
corresponding compound is known and may eas-
ily be synthesized by other means, for example,
a reaction of p-hydroquinone with 6-chloro-6H-
dibenzo[c,e][1,2]oxaphosphinine (DOP-Cl) [34].
Moreover, O-phosphorylated p-hydroquinones
obtained in a similar manner undergo rearrange-
ment by lithium diisopropylamide (LDA) catalysis,
resulting in 2,5-substituted derivatives, as described
for diethyl phosphite [26] and diphenylphosphine
oxide [35].
CONCLUSIONS
A
new synthetic approach to difunctional
phosphorus-containing quinones and variety
a
Heteroatom Chemistry DOI 10.1002/hc

New Phosphorus-Containing Quinone Derivatives
7
of correspondent derivatives has been presented.
The procedure turned out to lead selectively to
2,3-substituted p-hydroquinones. The presented
method proved to be convenient and efficient
for the synthesis of new aromatic diols suitable as
comonomer units of significantly higher phosphorus
content that will allow the preparation of polymers
with increased flame retardancy or a lower load of
additives for the same effect.
Synthesis
Diphenyl
(2,5-dihydroxyphenyl)phosphonate
((PhO)2PO-HQ, 1a). Diphenylphosphite (50.0 g,
215 mmol) was dissolved in 100 mL of toluene in
a three-necked flask equipped with a condenser
and an argon gas inlet. p-Benzoquinone (30.0 g,
277 mmol) was added in portions to the reaction
mixture over a period of 10 min at room temper-
ature. The reaction mixture was heated using an
oil bath to 65◦C, stirred at this temperature over
a period of 48 h and cooled to room temperature.
The solvent was removed at reduced pressure.
A solution of the residue in dichlormethane was
filtered through a small pad of silica gel, and the
filtrate was concentrated by the removal of solvent
at reduced pressure. After recrystallization from
toluene followed by drying at reduced pressure at
EXPERIMENTAL
Materials and Measurements
Unless stated otherwise, solvents and chemicals
were obtained from commercial sources and used as
received. DDPO was synthesized from neopentyl gly-
col and dimethyl phosphite as previously described
[36].
◦
80 C for 12 h, (PhO)2PO-HQ was obtained as beige
crystals (8.9 g, 26 mmol, 12%): mp 149-150◦C; 31P
NMR (101 MHz, DMSO-d6) δ 13.0; 13C NMR (63
MHz, DMSO-d6) δ 152.7 (d, J = 2.0 Hz, 1C), 150.1
(d, J = 6.8 Hz, 1C), 149.4 (d, J = 19.2 Hz, 1C), 129.8
(s, 4C), 125.0 (s, 2C), 122.9 (d, J = 2.5 Hz, 1C), 120.4
(d, J = 4.5 Hz, 4C), 119.6 (d, J = 9.4 Hz, 1C), 117.6
(d, J = 12.9 Hz, 1C), 111.2 (d, J = 186.9 Hz, 1C P);
1H NMR (250 MHz, DMSO-d6) δ 9.93 (s, 1H, OH),
9.16 (s, 1H, OH), 7.47–7.29 (m, 4H), 7.29–7.07 (m,
7H), 7.00–6.80 (m, 2H); IR (KBr) ν 3319 (s, O H),
NMR spectra were recorded with a Bruker (Bel-
lerica, MA) Analytical BZH 250/52 (250 MHz) and
a Varian (Palo Alto, CA) INOVA-400 (400 MHz).
Chemical shifts are given as δ values with internal
standard via solvent. 31P NMR spectra were mea-
sured proton decoupled, 13C NMR proton decou-
1
pled and phosphorus coupled and H NMR phos-
phorus coupled. IR spectra were recorded with a
Varian 660-IR (FT-IR). Melting points were mea-
sured with a Bu¨chi (Flawil, Switzerland) B-545 (un-
corrected). High-resolution mass spectra were ob-
tained with a MicroMass (Beverly, MA) GCT (EI,
70 eV) and a Bruker microTOF (ESI). Elementary
analysis (CHNS) was performed with an Elementar
(Hanau, Germany) VarioEL.
=
3065 (w, Caryl H), 1589 (m, C C), 1490 (vs, P Caryl),
=
1276 (m, C O), 1236, 1207, 1182 (s, P O), 1157,
1078, 955, and 943 (vs, P O), 774 and 747 (s, C H),
691, 603, 511; HRMS (EI) calcd for [12C18H15O5P]+
342.0657, found 342.0609. Anal calcd for C11H15O5P:
C 63.16, H 4.42; found: C 63.05, H 4.39.
Crystallographic Data
Tetraphenyl(3, 6 - dihydroxy - 1, 2 - phenylene)bis-
(phosphonate) ((PhO)2PO-2-HQ, 2a). Diphenyl
phosphite (250.0 g, 1068 mmol) and p-benzoquinone
(150.0 g, 1389 mmol) in 300 mL of toluene were
stirred in a round-bottomed flask equipped with
a condenser and an argon gas inlet at room tem-
perature over a period of 7 days. The solvent was
removed at reduced pressure. A solution of the
residue in dichlormethane was filtered through a
small pad of silica gel, and the filtrate was con-
centrated by the removal of solvent at reduced
pressure. After recrystallization from acetonitrile,
(PhO)2PO-2-HQ was obtained as white crystals
(153.3 g, 267 mmol, 25%): mp 93–94◦C; 31P NMR
(101 MHz, CDCl3) δ 15.0; 13C NMR (63 MHz, CDCl3)
δ 158.8 (t, J = 11.3 Hz, 2C), 149.8 (t, J = 3.9 Hz,
4C), 129.7 (s, 8C), 128.7 (t, J = 6.7 Hz, 2C), 125.5 (s,
4C), 120.2 (t, J = 2.4 Hz, 8C), 104.0 (dd, J = 189.4
XRD measurements were performed using
a
Siemens SMART CCD 1000 diffractometer with
monochromated Mo Kα irradiation collecting a full
sphere of data in the θ range from 1.57 to 28.34◦.
Frames were collected with an irradiation time of 20
or 10 s per frame and ω scan technique with ꢀω =
0.45◦. Data were corrected to Lorentz and polariza-
tion effects, and an empirical adsorption correction
with SADABS [37] was applied. The structures were
solved by direct methods and refined to an optimum
R1 value with SHELX-97 [38]. Visualization for eval-
uation was performed with XPMA [39], and figures
were created with Mercury [40].
CCDC numbers 856366–856376 contain the sup-
plementary crystallographic data for this paper.
These data can be obtained free of charge from
The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data request/cif.
1
Hz, J = 7.4 Hz, 2C P); H NMR (250 MHz, CDCl3)
Heteroatom Chemistry DOI 10.1002/hc

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Mu¨ller et al.
δ11.50 (s, 2H, 2OH), 7.29–7.12 (m, 22H); IR (KBr) ν
3435 (m, O H), 3015, 2980, and 2928 (m, Caryl H),
2.25 Hz, 1H, arom); 6.85 (dd, J1 = 12.00 Hz, J2 =
2.50 Hz, 1H, arom); 6.76 (t, J = 8.00 Hz, 1H, arom);
4.04 (t, J = 10.25 Hz, 2H, CH2 ); 3.97 (d, J = 3.50
Hz, 2H, CH2 ); 1.12 (s, 3H, CH3); 0.90 (s, 3H,
CH3). IR (KBr) ν 1453 (s, P Caryl); 1387 (w); 1225
=
1587 (s, C C), 1489 and 1437 (vs, P Caryl), 1263 (s,
=
C O), 1189 (vs, P O), 1154, 1135, 1026, 1010, 966,
959, and 941 (vs, P O), 768 and 749 (s, C H), 688,
635; HRMS (EI) calcd for [12C30H24O8P2]+ 574.0946,
found 574.0938. Anal calcd for C30H24O8P2: C 62.72,
H 4.21; found: C 62.71, H 4.21.
=
(vs, P O);1083 (m); 1059 (s, P O alkyl); 1008 (m);
833 (m); 778 (m); 531 (w). HRMS (ESI) calcd for
[12C11H15O5P + H]+ 259.0735, found 259.0722. Anal
calcd for C11H15O5P: C 51.17, H 5.86; found: C 50.75,
H 5.75.
2 - (2, 5 - Dihydroxyphenyl) - 5, 5 - dimethyl - 1, 3, 2 -
dioxaphosphinane 2-oxide (DDPO-HQ,1b) and
2,2ꢁ-(3,6-dihydroxy-1,2-phenylene)bis(5,5-dimethyl-
1,3,2-dioxaphosphinane 2-oxide) (DDPO-2-HQ, 2b).
DDPO (25.02 g, 0.167 mol) was dissolved in 120 mL
of dry toluene in a three-necked flask equipped with
a condenser and an argon inlet. p-Benzoquinone
(18.02 g, 0.167 mol) was added in portions during
a 2-h period at 75◦C. The mixture was refluxed
for an additional 2 h and allowed to cool down.
The liquid phase was decanted and was kept for
isolation of DDPO-1-HQ. The residue was refluxed
in 150 mL of 2-ethoxyethanol for 30 min and
allowed to cool down to room temperature. A white
solid (DDPO-2-HQ, 2b) was collected by filtration
at reduced pressure, washed with ethyl acetate,
and air-dried. Yield: 10.23 g (30.15%). mp: 260◦C
decomp. 31P NMR (101 MHz, DMSO-d6): 9.69 (s).
13C NMR (63 MHz, DMSO-d6): 154.4 (t, J = 9.7 Hz,
2C); 123.6 (t, J = 3.5 Hz, 2C); 113.3 (dd, J = 174.6
Hz, J = 9.7 Hz, 2C); 76.9 (s, 4C); 31.6 (t, J = 2.6 Hz,
2-(6-Oxido-6H-dibenzo[c,e][1,2]oxaphosphinine-
6-yl)-cyclohexa-2,5-diene-1,4-dione(DOPO-BQ,4).
2-(6-Oxido-6H-dibenzo[c,e][1,2]oxaphosphinin-6-
yl)-benzene-1,4-diol (DOPO-HQ, 9.73 g, 30 mmol)
and manganese dioxide (ca. 25 g) were suspended
in 200 mL of acetone and vigorously stirred for 1 h
at room temperature. The solid phase was collected
by filtration at reduced pressure and thoroughly
washed with acetone. To the combined filtrates,
10 g of charcoal was added and stirred for 30 min.
After filtration, the liquid phase was diluted with
diethyl ether to precipitate the product. The bright
orange solid was collected by filtration at reduced
pressure, and air-dried. Yield: 6.65 g (68.8%) mp:
195◦C decomp. 31P NMR (101 MHz, DMSO-d6):
16.77 (s). 13C NMR (63 MHz, DMSO-d6): 186.3 (d, J
= 15.9 Hz, 1C); 185.8 (d,J = 8.5 Hz, 1C), 149.0 (d,J
= 13.7 Hz, 1C); 144.6 (d, J = 3.3 Hz, 1C); 137.7 (s,
1C); 137.3 (d, J = 7.4 Hz, 1C); 135.9 (d, J = 1.8 Hz,
1C); 135.4 (d, J = 6.2 Hz, 1C); 134.5 (s, 1C); 131.5
(d,J = 13.8 Hz, 1C); 129.1 (d, J = 14.5 Hz, 1C);
126.0 (s, 1C); 125.3 (s, 1C); 124.4 (d, J = 10.1 Hz,
1C), 124.3 (d, J = 168.4 Hz, 1C); 123.1 (d,J = 132.1
Hz, 1C); 121.3 (d, J = 11.5 Hz, 1C); 120.1 (d,J = 6.6
1
2C); 21.9 (s, 2C); 20.0 (s, 2C). H NMR (250 MHz,
DMSO-d6): 9.87 (s, 2H, arom OH); 7.06 (t, J = 3.75
Hz, 2H, arom.); 3.70 (dd, J1 = 22.8 Hz, J2 = 11.25
Hz, 4H, CH2 axial), 3.45 (d, J = 11.0 Hz, 4H,
CH2 equatorial), 1.16 (s, 6H, CH3 axial); 0.60 (s,
6H, CH3 equatorial). IR (KBr) ν 1477 (m, P Caryl);
1
Hz, 1C). H NMR (250 MHz, DMSO-d6): 8.27 (m,
=
1335 (m); 1244 (s, P O); 1057 (s, P O alkyl); 1012
2H, arom.); 8.95–7.78 (m, 2H, arom.); 7.58 (m, 1H,
arom.); 7.47 (m, 1H, arom.); 7.32 (m, 2H arom. +
1H quinone); 6.87 (d, J = 40 Hz, 2H, quinone). IR
(m); 798 (m); 571 (m); 508 (m). HRMS (ESI) calcd
for [12C16H24O8P2]+ 406.0946, found 406.0996. Anal
calcd for C16H24O8P2: C 47.30, H 5.95; found: C
47.06, H 5.96.
=
(KBr) ν 3052 (w, C H aryl); 1664 (s, C O); 1539 (w,
=
C C); 1749 (m, P Caryl); 1325 (m); 1280 (w); 1232
The filtered 2-ethoxyethanol was completely
evaporated, and the residue was refluxed in chloro-
form for 30 min. After cooling down to room temper-
ature, a white solid (DDPO-1-HQ,1a) was collected
by filtration at reduced pressure, washed with chlo-
roform, and air-dried. Yield: 12.75 g (35.48%). mp:
185–189◦C. 31P NMR (101 MHz, DMSO-d6): 12.66 (s).
13C NMR (63 MHz, DMSO-d6): 153.2 (s, 1C); 150.2 (d,
J = 11.2 Hz, 1C); 122.3 (s, 1C); 118.9 (d,J = 5.0 Hz,
1C, C H arom); 118.3 (d, J = 7.7 Hz, 1C); 112.9 (d,
J = 113.9 Hz, 1C); 76.6 (s, 1C); 76.5 (s, 1C); 32.7
=
(s, P O); 1122 (m); 1100 (m); 926 (s, P O Caryl);
826 (m); 753 (C H arom bend.). HRMS (ESI) calcd
for [12C18H11O4P]+ 322.0395, found 322.0466. Anal
calcd for C18H11O4P: C 67.09, H 3.44; found C 66.65,
H 3.51.
6, 6ꢁ - (3, 6 - Dihydroxy - 1, 2 - phenylene)bis(6H -
dibenzo[c,e][1,2]oxaphosphinine 6-oxide (DOPO-2-
HQ, 3). DOPO-BQ (966 mg, 3 mmol) and DOPO
(649 mg, 3 mmol) were fed into a flame-dried flask
equipped with a condenser and an argon inlet and re-
fluxed in 25 mL of dry toluene for 3 h until the orange
color of the mixture completely faded. The product
1
(d, J = 4.1 Hz, 1C); 22.0 (s, 1C); 21.0 (s, 1C). H
NMR (250 MHz, DMSO-d6): 9.63 (s, 1H, arom OH);
9.14 (s, 1H, arom OH); 6.92 (dd,J1 = 15.75 Hz, J2 =
Heteroatom Chemistry DOI 10.1002/hc

New Phosphorus-Containing Quinone Derivatives
9
was collected by filtration at reduced pressure,
washed with toluene and dried at reduced pressure
and 100◦C for 2 days. Yield: 1380 mg (85.7%). White
solid. mp: 240–242◦C. 31P NMR (101 MHz, CDCl3):
34.66 (s, isomer 3a); 33.51 (s, isomer 3b) in a ratio
1:1.5. 1H NMR (250 MHz, CDCl3): 12.26 (s, 2H, aryl-
OH); 7.85–6.75 (m, 16H, arom); 6.67 (s, 1.20 H, C H
quinone isomer 3b); 5.93 (s, 0.80 H, C H quinone
isomer 3a). IR (KBr) ν 3065 (w, C H aryl); 1582 (w,
Diphenyl
(3,6-dihydroxy-2-(6-oxido-6H-
dibenzo[c, e][1, 2]oxaphosphinin - 6 - yl)phenyl)phos -
phonate (DOPO-HQ-(PhO)2PO, 5). DOPO-BQ (966
mg, 3 mmol) and diphenyl phosphite (703 mg, 3
mmol, 574 μl) were fed into a flame-dried flask
equipped with a condenser and an argon inlet and
refluxed in 25 mL of dry toluene for 3 h. The hot
solution was quickly withdrawn, allowed to cool
down to room temperature, and left overnight.
The product precipitated as colorless crystals, was
collected by filtration at reduced pressure, and air-
dried. Yield: 834 mg (50.0%). mp: 181◦C. 31P NMR
(101 MHz, DMSO-d6): 32.45 (s, P DOPO); 10.25 (s, P
phosphite, isomer a); 10.14 (s, P phosphite, isomer
b). 13C NMR (101 MHz, DMSO-d6): 159.5 (1C); 159.1
(d, J = 4.9 Hz, 1C); 156.8 (d, J = 14.2 Hz, 1C); 150.3
(dd, J1 = 18.1 Hz, J2 = 6.2 Hz, 2C); 134.9 (d, J =
4.4 Hz, 1C), 132.9 (s, 1C); 130.9 (s, 1C); 130.2 (d, J
= 2.6 Hz, 4C); 128.8 (d, J = 14.1 Hz, 1C); 127.8 (d,
J = 12.4 Hz, 1C); 127.5 (d, J = 13.1 Hz, 1C); 125.8
(s, 1C); 125.7 (d, J = 135 Hz, 1C); 125,6 (s, 2C);
124.8 (s, 1C); 123.9 (d, J = 9.8 Hz, 2C); 121.8 (d, J =
12.5 Hz, 1C); 120.9 (s, 4C); 120.5 (d, J = 6.7 Hz, 1C);
=
C C); 1475 (m, P Caryl); 1446 (s, P Caryl); 1271 (m,
=
P O); 1190 (s, P O aryl); 947 (s, P O Caryl); 751 (s,
C H arom bend.); 634 (m). HRMS (ESI) calcd for
[12C30H20O6P2]+ 538.0735, found 538.0787.
The isomers were separated by column chro-
matography on silica gel using dichloromethane as
an eluent (TLC: isomer 3a: R = 0.36; isomer 3b: R
f
f
= 0.29).
Isomer 3a: Colorless crystals after recrystalliza-
tion from acetonitrile. mp: 277–279◦C 31P-NMR (101
MHz, CDCl3): 34.66 (s). 13C NMR (63 MHz, CDCl3):
161.6 (t, J = 10.0 Hz, 2C); 146.5 (t, J = 4.2 Hz, 2C);
133.65 (d, J = 2.6 Hz, 2C); 132.5 (s, 2C); 129.7 (t,
J = 5.2 Hz, 2C); 129.3 (s, 2C); 129.2 (t, J = 7.0 Hz,
2C); 128.6 (t,J = 5.1 Hz, 2C); 126.7 (d, J = 137.6
Hz, 2C); 124.8 (s, 2C); 124.0 (t, J = 5.0 Hz, 2C);
124.0 (s, 2C); 121.6 (t, J = 6.4 Hz, 2C); 120.5 (t,
J = 3.1 Hz, 2C); 102.6 (dd,J1 = 142.5 Hz,J2 = 9.3
1
110.4 (dd, J1 = 187.0 Hz,J2 = 9.2 Hz, 2C), H NMR
(250 MHz, DMSO-d6): 12.04 (s, 1H, aryl-OH); 10.88
(s, 1H, aryl-OH); 8.22 (t, J = 7.5 Hz, 2H, arom); 7.66
(t, J = 6.3 Hz, 1H, arom); 7.50–7.05 (13H, arom);
6.98 (d, J = 8.0 Hz, 2H, arom); 6.78 (d,J = 7.8 Hz,
2H, arom). IR (KBr) ν 3052 (w, C H aryl); 1590
1
Hz, 2C). H NMR (250 MHz, CDCl3): 12.23 (s, 2H,
aryl-OH); 7.73 (m, 4H, arom.); 7.52 (m, 3H, arom.);
7.45 (m, 5H, arom.); 6.94 (m, 4H, arom.); 5.93 (d,
J = 8.0 Hz, 2H, C H quinone). IR (KBr) ν 3062 (w,
=
(w, C C); 1490 (m, P Caryl); 1447 (s, P Caryl); 1271
=
=
(m, P O DOPO); 1201 (s, P O aryl); 1180 (s, P O
(PhO)2PO); 965 (s, P O Caryl); 953(s, P O Caryl);
761 (s, C H arom. bend.); 633 (m). HRMS (ESI)
calcd for [12C30H22O7P2]+ 556.0841, found 556.0896.
Anal calcd for C30H22O7P2: C 64.75, H 3.99; found: C
64.75, H 4.09.
=
C H aryl); 1583 (w, C C); 1477 (m, P Caryl), 1445 (s,
=
P Caryl); 1269 (m, P O); 1190 (s, P O aryl); 942 (s,
P O Caryl); 748 (s, C H arom. bend.); 636 (m). Anal
calcd for C30H20O6P2: C 66.92, H 3.74; found: C 66.77,
H 3.72.
Isomer 3b: Colorless crystals after recrystalliza-
tion from acetonitrile. mp: 272–275◦C 31P NMR (101
MHz, CDCl3): 33.51 (s). 13C NMR (63 MHz, CDCl3):
161.7 (t, J = 9.7 Hz, 2C); 147.9 (t, J = 4.2 Hz, 2C);
133.8 (d, J = 2.5 Hz, 2C); 132.3 (s, 2C); 130.2 (s,
2C); 129.6 (t, J = 5.2 Hz); 128.9 (t, J = 6.9 Hz, 2C);
127.8 (t, J = 7.8 Hz, 2C); 124.5 (s, 2C); 124.3 (s, 2C);
123.7 (d, J = 135.0 Hz, 2C); 123.2 (t, J = 5.1 Hz, 2C);
121.3 (t, J = 6.1 Hz; 2C); 120.8 (t,J = 3.2 Hz; 2C);
103.3 (dd, J1 = 142.5 Hz, J2 = 9.1 Hz, 2C). 1H NMR
(250 MHz, CDCl3): 12.25 (s, 2H, aryl-OH); 7.48 (m,
2H, arom.); 7.42, 2H, arom.); 7.32 (m, 4H, arom.);
7.12 (m, 4H, arom.); 6.90 (m, 4H, arom.); 6.64 (d, J
= 7.5 Hz, 2H, C H quinone). IR (KBr) ν 3062 (w,
6-(2-(Diphenylphosphoryl)-3,6-dihydroxyphenyl)-
6H-dibenzo[c,e][1,2]oxaphosphinine 6-oxide (DOPO-
HQ-DPhPO,6). DOPO-BQ (1.61 g, 5 mmol) and
diphenylphosphine oxide (1.01 g, 5 mmol) were
processed in the manner described above for DOPO-
2-HQ to obtain a white solid, yield 1.72 g (65.8%).
mp: 228–230◦C 31P NMR (101 MHz, CDCl3): 47.52
(s); 32.17 (s). 13C NMR (101 MHz, CDCl3): 162.6 (d,
J = 13.8 Hz, 2C); 145.8 (d,J = 6.3 Hz, 1C); 133.1 (d,
J = 3.7 Hz, 1C); 132.9 (d, J = 7.5 Hz, 4C); 132.3 (s,
2C, Ph), 131.7 (d, J = 113.6 Hz, 2C); 131.1 (s, 1C);
130.2 (s, 1C); 129.9 (d, J = 10.8 Hz, 1C); 128.4–128.1
(m, 5C); 127.5 (d, J = 12.8 Hz, 1C); 127.1 (d, J =
12.8 Hz); 125.4 (d, J = 134.3 Hz, 1C); 125.1 (s, 1C);
124.3 (s, 1C); 124.1 (d, J = 9.6, 1C); 122.5 (d, J =
12.1 Hz, 1C); 120.2 (d, J = 5.8 Hz, 1C); 110.2 (d, J
=
C H aryl); 1582 (w, C C); 1475 (m, P Caryl); 1444
=
(s, P Caryl); 1271 (s, P O); 1190 (s, P O aryl); 948
(s, P O Caryl); 751 (s, C H arom bend.); 633 (m).
Anal calcd for C30H20O6P2: C 66.92, H 3.74; found: C
67.04, H 3.78.
1
= 322.6 Hz, 2C). H NMR (250 MHz, CDCl3): 13.02
(s, 1H, OH); 11.18 (s, 1H, OH); 7.92 (dd, J1 = 3.1
Heteroatom Chemistry DOI 10.1002/hc

10 Mu¨ller et al.
Hz, J2 = 1.8 Hz, 2H arom.); 7.72 (d, J = 1.8 Hz, 1H,
arom.); 7.63 (m, 3H, arom.); 7.47 (m, 2H, arom.);
7.34 (m, 3H, arom.); 7.27 (s, 1H arom.); 7.14 (t, J
= 0.9 Hz, 2C, arom.); 6.92 (m, 3H, arom.); 6.50 (s,
2H, arom.); 5.86 (s, 1H, arom.). IR (KBr) ν 3052
(w, C H aryl); 1463 (s, P Caryl); 1354 (m); 1277
and concentrated at reduced pressure. A solution of
the residue in dichloromethane was filtered through
a small pad of silica gel, and the filtrate was concen-
trated by complete removal of the solvent at reduced
pressure. After recrystallization from cyclohexane,
(PhO)2PO-HQ-rear was obtained as beige crystals
(5.8 g, 17 mmol, 39%): mp 96–97◦C; 31P NMR (101
MHz, CDCl3) δ −16.2; 13C NMR (63 MHz, CDCl3) δ
154.3 (s, 1C), 150.2 (d, J = 7.6 Hz, 1C), 142.9 (d, J =
7.6 Hz, 1C), 129.6 (s, 4C), 125.7 (s, 2C), 120.8 (d, J =
4.5 Hz, 2C), 120.0 (d, J = 4.9 Hz, 4C), 116.4 (s, 3C);
1H NMR (250 MHz, CDCl3) 7.67 (s, 1H, OH), 7.42–
7.18 (m, 10H, 2Ph), 6.95 (d, J = 8.1 Hz, 2H), 6.62 (d,
J = 8.8 Hz, 2H); IR (KBr) ν 3247 (s, O H), 3057 and
=
(m, P O of DOPO unit); 1205 (s, P O aryl); 1118
=
(s, P O of DPhPO unit); 948 (s, P O Caryl); 750
(s, C H arom. bend.); 627 (m). HRMS (ESI) calcd
for [12C30H22O5P2]+ 524.0943, found 524.0989. Anal
calcd for C30H22O5P2: C 68.71, H 4.23; found: 68.59,
H 4.27.
6-(2-(5,5-Dimethyl-2-oxido-1,3,2-dioxaphosph-
inan-2-yl)-3,6-dihydroxyphenyl)-6H-dibenzo[c,e]
[1,2]oxaphosphinine 6-oxide (DOPO-HQ-DDPO,7).
DOPO-BQ (1.61 g, 5 mmol) and DDPO (826 mg,
5.5 mmol) were processed in the manner described
above for DOPO-2-HQ to obtain a white solid, yield
1.30 g (55.1%). mp: 133–134◦C. 31P NMR (101 MHz,
CDCl3): 33.36 (s, P DOPO, isomer a); 33.27 (s, P
DOPO, isomer b); 15.11 (s, P DDPO). 13C NMR (101
MHz, CDCl3): 161.1 (s, 1C); 154.7 (d, J = 23.9 Hz,
1C); 149.0 (d, J = 8.0 Hz, 1C); 134.8 (s, 1C); 132.8
(s, 1C); 130.4 (s, 1C); 129.7 (d, J = 13.3 Hz, 1C);
128.1 (d, J = 14.0 Hz, 1C); 127.6 (d, J = 12.1 Hz,
1C); 125.8 (d, J = 153.2 Hz, 1C); 124.7 (s, 1C); 124.
6 (1C); 123.0 (s, 1C); 122.9 (s, 1C); 121.5 (d, J =
12.1 Hz, 1C); 120.8 (d, J = 6.1 Hz, 1C); 114.0 (d,
J = 193 Hz, 2C); 75.6 (s, 1C); 75.2 (s, 1C); 32.4 (s,
=
3038 (w, Caryl H), 1601 and 1587 (m, C C), 1507,
1488, 1456, 1262 (s, C O), 1215, 1185 and 1167 (s-
=
vs, P O), 1152, 1026, 1011, 989 and 972 (vs, P O),
939, 837, 769, and 757 (s, C H), 688, 579, 546, 521,
504; HRMS (EI) calcd for [12C18H15O5P]+ 342.0657,
found 342.0605. Anal calcd for C18H15O5P: C 63.16,
H 4.42; found: C 63.26, H 4.42.
2-(3-(5,5-Dimethyl-2-oxido-1,3,2-dioxaphosph-
inane-2-yl)-4-hydroxyphenoxy)-5,5-dimethyl-1,3,2-
dioxaphosphinane 2-oxide (DDPO-2-HQ-rear, 9b).
DDPO-2-HQ (0.50 g, 1.23 mmol) and 3 mL of tri-
ethylamine in 20 mL of acetonitrile were refluxed in
a round-bottomed flask equipped with a condenser
over a period of 3 days. The reaction mixture was
cooled with an ice bath. The formed precipitate was
collected by filtration at reduced pressure, washed
with acetonitrile, and dried at air to give the required
product DDPO-2-HQ-rear as an off beige solid (0.35
g, 0.85 mmol, 69%). mp: 218–219◦C; 31P NMR (101
MHz, CDCl3) δ 18.4 (s), −12.9 (s); 13C NMR (63 MHz,
CDCl3) δ159.3 (d, J = 7.0 Hz, 1C), 142.5 (dd, J = 19.5
Hz, J = 6.7 Hz, 1C), 127.3 (dd, J = 2.6 Hz, J = 5.4
Hz, 1C), 121.6 (dd, J = 7.1 Hz, J = 4.7 Hz, 1C), 119.3
(d, J = 14.4 Hz, 1C), 108.3 (d, J = 194.1 Hz, 1C P),
78.4 (d, J = 7.0 Hz, 2C), 75.7 (d, J = 6.2 Hz, 2C), 32.6
(d, J = 6.3 Hz, 1C), 32.2 (d, J = 6.0 Hz, 1C), 22.0 (s,
1
1C); 21.8 (s, 1C); 21.3 (s, 1C). H NMR (250 MHz,
CDCl3): 12.13 (s, 1H, OH); 8.61 (s, 1H, OH); 8.09 (t,
J = 7.0 Hz, 2H, C H arom.); 7.68 (t, J = 6.5 Hz,
1H, C H arom.); 7.57 (d, J = 15.5 Hz, 1C, C H
arom.); 7.43 (m, 2H, C H arom.); 7.27 (t, J = 7.5
Hz, 2H, C H arom.); 7.18 (d, J = 6.8 Hz, 2H, C H
quinone); 3.81 (d, J = 39.0 Hz, 2H, CH2 ); 3.40
(d,J = 38.8 Hz, 2H, CH2 ); 0.87 (s, 3H, CH3);
0.78 (s, 3H, CH3). IR (KBr) ν 3064 (w, C H aryl);
=
1559 (w, C C); 1465 (s, P Caryl); 1359 (m); 1276
=
=
(vs, P O DOPO); 1223 (vs, P O DDPO); 1195 (vs,
P O aryl); 1071 (vs, P O alkyl); 943 (P O Caryl);
747 (s, C H arom. bend.); 627 (s). HRMS (ESI)
calcd for [12C23H22O7P2]+ 472.0841, found 472.0846.
Anal calcd for C23H22O7P2: C 58.48, H 4.69; found: C
58.41, H 4.63.
1
1C), 21.6 (s, 1C), 21.4 (s, 1C), 20.2 (s, 1C); H NMR
(250 MHz, CDCl3) δ9.98 (s, 1H, OH), 7.43 (d, J = 16.0
Hz, 1H), 7.30 (dd, J = 2.2 Hz, J = 9.0 Hz, 1H), 6.93
(d, J = 8.4 Hz, 1H), 4.41 (dd, J = 4.8 Hz, J = 10.9 Hz,
2H), 4.21 (d, J = 10.3 Hz, 2H), 4.03 (d, J = 11.3 Hz,
2H), 3.95 (d, J = 10.7 Hz, 2H), 1.34 (s, 3H, CH3), 1.31
(s, 3H, CH3), 1.02 (s, 3H, CH3), 0.90 (s, 3H, CH3); IR
(KBr) ν 3431 (m, O-H), 3055 (m, Caryl H), 2972 (m,
4-Hydroxyphenyl diphenyl phosphate ((PhO)2PO-
HQ-rear, 8a). A three-necked flask with a con-
denser, a thermometer, and an argon gas inlet was
flooded with argon and charged with diphenylphos-
phite (10.0 g, 43 mmol), p-benzoquinone (6.0 g, 56
mmol), and 30 mL of toluene. The reaction mix-
ture was cooled with an ice bath to 5◦C and triethy-
lamine (2.5 g, 11 mmol) was added. The reaction
mixture was stirred at room temperature overnight
=
Calkyl H), 1605 (w, C C), 1497 and 1473 (m, P Caryl),
1418 (s), 1375, 1295 (vs, C O), 1216 and 1194 (s-vs,
=
P O), 1088, 1062 (vs, P O), 1021, 993, and 954 (s,
P O Caryl), 880, 853, 836, 567, 490; HRMS (EI) calcd
for [12C16H24O8P2]+ 406.0946, found 406.1052. Anal.
Heteroatom Chemistry DOI 10.1002/hc

New Phosphorus-Containing Quinone Derivatives 11
[4] Enders, D.; Saint-Dizier, A.; Lannou, M.-I.; Lenzen,
A. Eur J Org Chem 2006, 29–49.
[5] Enders, D.; Tedeschi, L.; Bats, J. W. Angew Chem, Int
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H 5.85.
6-(4-Hydroxy-3-(6-oxido-6H-dibenzo[c,e][1,2]-
oxaphosphinine-6-yl)phenoxy)-6H-dibenzo[c,e][1,2]-
oxaphosphinine
6-oxide
(DOPO-2-HQ-rear,10).
DOPO-2-HQ (0.20 g, 0.37 mmol) and 3 mL of
triethylamine in 20 mL of toluene were refluxed in
a round-bottomed flask equipped with a condenser
over a period of 5 days. The reaction mixture was
cooled to room temperature. The formed precipitate
was collected by filtration at reduced pressure,
washed with toluene, and dried at air to give the
required product DOPO-2-HQ-rear as an off-beige
solid (0.11 g, 0.20 mmol, 55%). mp: 251–253◦C; 31P
NMR (101 MHz, DMSO-d6) δ 20.4 (s), 7.7 (s); 13C
NMR (63 MHz, DMSO-d6) δ157.5 (d, J = 2.6 Hz,
1C), 149.3 (d, J = 8.5 Hz, 1C), 149.1 (d, J = 8.3 Hz,
1C), 140.7 (dd, J = 17.7 Hz, J = 8.7 Hz, 1C), 136.4
(d, J = 7.0 Hz, 1C), 134.8 (d, J = 5.8 Hz, 1C), 134.3
(s, 1C), 132.7 (s, 1C), 130.9 (s, 1C), 130.2 (s, 1C),
130.2 (d, J = 9.3 Hz, 1C), 129.9 (d, J = 12.8 Hz, 1C),
128.9 (d, J = 15.5 Hz, 1C), 128.3 (d, J = 14.0 Hz,
1C), 127.5 (m, 1C), 125.9 (s, 1C), 125.3 (s, 1C), 125.2
(s, 1C), 124.8 (s, 1C), 124.6 (m, 2C), 124.2 (s, 1C),
123.5 (d, J = 10.0 Hz, 1C), 120.8 (d, J = 133.8 Hz,
1C P), 120.3 (d, J = 169.9 Hz, 1C P), 119.1 (dd,
J = 210.6 Hz, J = 10.3 Hz, 1C P), 119.8 (d, J =
6.9 Hz, 1C), 119.6 (d, J = 7.3 Hz, 1C), 116.9 (s, 1C),
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1
114.6 (s, 1C); H NMR (250 MHz, DMSO-d6) δ10.34
(s, 1H, OH), 8.36–8.18 (m, 4H), 7.97–7.82 (m, 2H),
7.81–7.59 (m, 2H), 7.59–7.17 (m, 9H), 7.15–7.04
(m, 1H), 6.74–6.63 (m, 1H); IR (KBr) ν 3434 (m,
=
O H), 3069 (m, Caryl H), 1596 and 1584 (m, C C),
1478 (vs, P Caryl), 1448, 1431, 1415, 1276 (s, C O),
=
1241, 1195 (vs, P O), 1149, 1119, 960 and 932
(vs, P O), 864, 755 (vs, C H), 715, 619, 609, 524,
508; HRMS (EI) calcd for [12C30H20O6P2]+ 538.0735,
found 538.0736. Anal calcd for C30H20O6P2: C 66.92,
H 3.74; found: C 67.14, H 3.91.
ACKNOWLEDGMENTS
The authors would like to thank Dr. Olaf Fuhr and
Mr. Gilbert Zwick for measuring HR-MS, Ms. Ilona
Schmelcher for performing elementary analysis, and
Ms. Rebecca Lauber for measurement of IR spectra
and melting points.
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